CN105722800B - The manufacturing method of plate glass - Google Patents
The manufacturing method of plate glass Download PDFInfo
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- CN105722800B CN105722800B CN201480061692.9A CN201480061692A CN105722800B CN 105722800 B CN105722800 B CN 105722800B CN 201480061692 A CN201480061692 A CN 201480061692A CN 105722800 B CN105722800 B CN 105722800B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
- C03B25/08—Annealing glass products in a continuous way with horizontal displacement of the glass products of glass sheets
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
The present invention relates to a kind of plate glass manufacturing methods, it is to melt glass raw material and melten glass is made and the melten glass is configured to the glass tape of plate using building mortion and then the glass tape is carried out to the plate glass manufacturing method of slow cooling using annealing device, in the plate glass manufacturing method, the plate glass includes alkali-free glass, and the strain point of the alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of 50 DEG C, so that the SO directly below of the lower surface of the glass tape2And/or SO3The mode that the time that gas concentration reaches 500~20000ppm is 30 seconds or more supplies SO2And/or SO3Gas.
Description
Technical field
The present invention relates to be suitable as various base plate for displaying glass, base board for optical mask glass include alkali-free glass
Plate glass manufacturing method.
Hereinafter, referring to alkali metal oxide (Li in the case where mentioning " alkali-free " in the present specification2O、Na2O、K2O)
Content be 2000 molar ppms below.
Background technology
In the past, metal or sull etc. were formed with for various base plate for displaying glass, particularly on surface
Base plate for displaying glass, it is desirable that characteristic as shown below.
(1) when containing alkali metal oxide, alkali metal ion is diffused into film and membrane property is made to deteriorate, it is therefore desirable to
The content of alkali metal oxide is extremely low, specifically, it is desirable that the content of alkali metal oxide is 2000 molar ppms or less.
(2) in film formation process be in high temperature when, in order to will with glass deformation and glass structure it is steady
Surely the contraction (thermal contraction) changed inhibits in minimum limit, it is desirable that strain point is high.
(3) it requires to form the middle various chemicals used with sufficient chemical durability to semiconductor.It is required that being especially
To used in the etching of the liquid containing hydrochloric acid, metal electrode that are used in the etching of ITO various sour (nitric acid, sulfuric acid etc.),
Alkali of anticorrosive additive stripping liquid controlling etc. has durability.
(4) internal and surface is required not have defect (bubble, brush line, field trash, dent, cut etc.).
Other than above-mentioned requirement, also following situation in recent years.
(5) lightweight of display is required, it is expected that glass itself is also the small glass of density.
(6) lightweight of display, expectation substrate glass is required to be thinned.
(7) other than non-crystalline silicon (a-Si) type liquid crystal display so far, it is slightly higher heat treatment temperature has also been made
Polysilicon (p-Si) type liquid crystal display (a-Si：About 350 DEG C → p-Si：350~550 DEG C).
(8) in order to accelerate make liquid crystal display heat treatment heating and cooling rate and improve productivity or raising
Thermal shock resistance, it is desirable that the small glass of the mean thermal expansion coefficients of glass.
On the other hand, the drying kinetics of etching promote, and the requirement to resistance to BHF weakens (BHF：Buffered hydrofluoric acid, hydrofluoric acid with
The mixed liquor of ammonium fluoride).Glass so far uses the B containing 6~10 moles of % mostly in order to improve resistance to BHF2O3's
Glass.But B2O3In the presence of the tendency for reducing strain point.As without B2O3Or the example of poor alkali-free glass, have as follows
The glass.
The B containing 0~3 weight % is disclosed in patent document 12O3Glass, but the strain point of embodiment be 690 DEG C with
Under.
The B containing 0~5 mole of % is disclosed in patent document 22O3Glass, but the evenly heat at 50~300 DEG C is swollen
Swollen coefficient is more than 50 × 10-7/℃。
In order to solve the problems in glass described in Patent Documents 1 to 2 point, it is proposed that the nothing described in patent document 3
Alkali glass.The strain point of alkali-free glass described in Patent Document 3 is high, can be formed using float glass process, be considered suitable for showing
Show the purposes such as device substrate, base board for optical mask.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 4-325435 bulletins
Patent document 2：Japanese Unexamined Patent Publication 5-232458 bulletins
Patent document 3：Japanese Unexamined Patent Publication 10-45422 bulletins
Patent document 4：Japanese table patent 2009-148141 bulletins public again
Invention content
Problem to be solved by the invention
But the manufacturing method of the p-Si TFT as high-quality, there is solid-phase crystallization method, but in order to implement this method,
It asks and further increases strain point.
On the other hand, it needs to consider from technology for making glass, particularly fusing, forming, it is desirable that reduce the viscous of glass
Property, particularly glass viscosity reach 104Temperature T when dPas4。
In addition, for the purpose for the damage for preventing from being configured to the glass tape after plate, it is known that following technology：In leer
To the glass tape injection sulfurous acid (SO after forming2) gas, to form the loss prevention for including sulfate in the lower surface of glass tape
Wound protective layer (referring to patent document 4).
But in the case of alkali-free glass, it is difficult to antisitic defect protective layer is effectively formed on glass tape, although into
The research of equipment aspect is gone, but occasionally there are the restrictions etc. that equipment is constituted.
The purpose of the present invention is to provide solve disadvantages mentioned above, strain point is high and low viscosity, particularly glass viscosity reach
To 104Temperature T when dPas4It is low and can be effectively formed comprising sulfate on the glass tape after being configured to plate
The manufacturing method of the plate glass comprising alkali-free glass of antisitic defect protective layer.
The means used to solve the problem
The present invention provides a kind of plate glass manufacturing method, wherein melts glass raw material and melten glass is made, and will
The melten glass is configured to the glass tape of plate using building mortion, and the glass tape is then carried out slow cooling using annealing device,
In above-mentioned plate glass manufacturing method,
Above-mentioned plate glass includes following alkali-free glasss,
The strain point of above-mentioned alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C,
So that the SO directly below of the lower surface of above-mentioned glass tape2Gas concentration reach 500~20000ppm time be 30 seconds with
On mode supply SO2Gas,
The strain point of above-mentioned alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7
~43 × 10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104dPa·s
When temperature T4For 1310 DEG C hereinafter, indicating that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.35 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
In addition, the present invention provides a kind of plate glass manufacturing method, wherein melt glass raw material and melting glass is made
Glass, and the melten glass is configured to the glass tape of plate using building mortion, then by the glass tape using annealing device into
Row slow cooling, in above-mentioned plate glass manufacturing method,
Above-mentioned plate glass includes following alkali-free glasss,
The strain point of above-mentioned alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C,
So that the SO directly below of the lower surface of above-mentioned glass tape3Gas concentration reach 500~20000ppm time be 30 seconds with
On mode supply SO3Gas,
The strain point of above-mentioned alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7
~43 × 10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104dPa·s
When temperature T4For 1310 DEG C hereinafter, indicating that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21, and
MgO/ (MgO+CaO+SrO+BaO) is 0.35 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
In addition, the present invention provides a kind of plate glass manufacturing method, wherein melt glass raw material and melting glass is made
Glass, and the melten glass is configured to the glass tape of plate using building mortion, then by the glass tape using annealing device into
Row slow cooling, in above-mentioned plate glass manufacturing method,
Above-mentioned plate glass includes following alkali-free glasss,
The strain point of above-mentioned alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C,
So that the SO directly below of the lower surface of above-mentioned glass tape2And SO3The time that gas concentration reaches 500~20000ppm is 30
Second or more mode supply SO2And SO3Gas,
The strain point of above-mentioned alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7
~43 × 10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104dPa·s
When temperature T4For 1310 DEG C hereinafter, indicating that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.35 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
Invention effect
In the plate glass manufacturing method of the present invention, the anti-of sulfate can be efficiently and uniformly formed on glass tape
Damage protective layer, and sulfurous acid (SO can also be saved2) and/or SO3The supply amount of gas.As a result, it is few to obtain damage
High-quality plate glass.
Base plate for displaying, base board for optical mask etc. of the plate glass of the present invention particularly suitable for high strain-point purposes.
Specific implementation mode
Hereinafter, being illustrated to the plate glass manufacturing method of the present invention.
In the manufacturing method of the plate glass of the present invention, the glass raw material for being deployed into following glass compositions is used.
It is indicated, is contained with mole % based on oxide
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.35 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 alkali-free glass below.
Next the compositing range of each ingredient is illustrated.SiO2Less than 63% (mole %, below as long as no special
Statement is then identical) when, the insufficient raising of strain point, and coefficient of thermal expansion increases, density increases.Preferably 64% or more, it is more excellent
It is selected as 65% or more, further preferably 66% or more, particularly preferably 66.5% or more.When more than 74%, melting reduces,
Glass viscosity reaches 102Temperature T when dPas2, glass viscosity reach 104Temperature T when dPas4It increases, devitrification temperature liter
It is high.Preferably 70% hereinafter, more preferably 69% hereinafter, further preferably 68% or less.
Al2O3When inhibiting the split-phase of glass, reduce coefficient of thermal expansion, improve strain point, but being less than 11.5%, do not show
As a result the effect thermally expands and increases in addition, increasing due to making other improve the ingredient of expansion.Preferably 12% or more, 12.5%
More than, further preferably 13% or more.But when more than 16%, it is possible to which the melting variation of glass makes devitrification temperature
Degree increases.Preferably 15% hereinafter, more preferably 14% hereinafter, further preferably 13.5% or less.
B2O3Improve the fusing reactivity of glass, reduce devitrification temperature, improve resistance to BHF, but when being 1.5% or less, it cannot
The effect is fully showed, in addition, strain point becomes excessively high, or the problem of easy to produce after the processing using BHF mist degree.It is excellent
It is selected as 2% or more, more preferably 3% or more.But when more than 5%, strain point reduces, and Young's modulus reduces.Preferably
4.5% hereinafter, more preferably 4% or less.
MgO has in alkali earths not to be improved expansion and is being kept as density lower to improve Young's modulus
Characteristic, and also melting is made to improve, but when less than 5.5%, cannot fully show the effect, and due to other alkali earths
Ratio improve, therefore density increase.Preferably 6% or more, further preferably 7% or more, more preferably 7.5% or more,
8% or more, even more preferably for more than 8%, preferably 8.1% or more, further preferably 8.3% or more, particularly preferably
It is 8.5% or more.When more than 13%, devitrification temperature increases.Preferably 12% hereinafter, more preferably 11% hereinafter, particularly preferably
It is 10% or less.
After CaO occupy MgO, has in alkali earths and do not improve expansion and density is kept as lower carry
The characteristic of high Young's modulus, and also melting is made to improve.When less than 1.5%, it cannot fully show above-mentioned CaO additions and be produced
Raw effect.Preferably 2% or more, more preferably 3% or more, further preferably 3.5% or more, particularly preferably 4% with
On.But when more than 12%, it is possible to which devitrification temperature increases, or a large amount of lime stone (CaCO being mixed into as CaO raw materials3)
In the phosphorus as impurity.Preferably 10% hereinafter, more preferably 9% hereinafter, further preferably 8% hereinafter, particularly preferably
It is 7% or less.
The devitrification temperature of glass is raised to improve melting to SrO in the case that not making, but when less than 1.5%, cannot be abundant
Show the effect.Preferably 2% or more, more preferably 2.5% or more, further preferably 3% or more.But more than 9%
When, it is possible to the coefficient of expansion increases.Preferably 7% hereinafter, more preferably 6% or less, 5% or less.
BaO is not essential, but can be contained to improve melting.But can make when excessive glass expansion and
Density too greatly increases, therefore is set as 1% or less.Preferably 0.5% hereinafter, more preferably 0.3% hereinafter, further preferably
For 0.1% hereinafter, particularly preferably essentially free of.Essentially free of referring to being free of other than inevitable impurity
Have (following same).
It can contain 2% below in order to reduce glass melting temperature or in order to promote crystal when firing to be precipitated
ZrO2.When more than 2%, glass becomes unstable or glass permittivity ε and increases.Preferably 1.5% hereinafter, more preferably
For 1% hereinafter, further preferably 0.5% hereinafter, particularly preferably essentially free of.
When MgO, CaO, SrO, BaO are less than 15.5% in the total amount, it is possible to glass viscosity be made to reach 104When dPas
Temperature T4Increase and make in float forming the service life of the shell structure object of float tank, heater extremely to shorten.Preferably 16%
More than, further preferably 17% or more.When more than 21%, it is possible to produce the difficult point of coefficient of thermal expansion can not be reduced.It is preferred that
For 20% or less, 19% hereinafter, further preferably 18%.
By making the total amount of MgO, CaO, SrO and BaO meet above-mentioned condition and meeting following conditions, devitrification can not made
Young's modulus, specific modulus and the viscosity, particularly T that reduce glass are improved in the case of temperature is raised4。
MgO/ (MgO+CaO+SrO+BaO) is 0.35 or more, preferably 0.37 or more, more preferably 0.4 or more.
CaO/ (MgO+CaO+SrO+BaO) is for 0.50 hereinafter, preferably 0.48 hereinafter, more preferably 0.45 or less.
SrO/ (MgO+CaO+SrO+BaO) is 0.50 hereinafter, preferably 0.40 hereinafter, more preferably 0.30 hereinafter, more excellent
0.27 is selected as hereinafter, further preferably 0.25 or less.
In the alkali-free glass of the present invention, Al2O3× (MgO/ (MgO+CaO+SrO+BaO)) is 4.3 or more due to that can carry
High Young's modulus and it is preferred that.Preferably 4.5 or more, more preferably 4.7 or more, further preferably 5.0 or more.
In the plate glass manufacturing method of the present invention, in order to improve the antisitic defect guarantor for forming sulfate on glass tape
Efficiency when sheath preferably makes to contain preferably 150 molar ppms or more in glass raw material, and it is more than more preferably 300 molar ppms,
It is further the alkali metal oxide of 500~2000 molar ppms.
In the present invention, by making to contain preferably 150 molar ppms or more in glass raw material, being more preferably 300 moles
Ppm or more, it is further alkali metal oxides more than 500 molar ppms, thus improves and form antisitic defect guarantor on glass tape
Efficiency when sheath.Its reason is as described below.The glass tape of high temperature is being exposed to SO2In the case of in gas atmosphere, preferably
More than 500 molar ppms.
Alkali-free glass does not contain alkali metal oxide, therefore, even if the glass tape of high temperature is exposed to SO2Gas and/or
SO3In gas atmosphere, the antisitic defect protective layer as obtained from the precipitation of alkali metal sulfates can not be also formed.For a large amount of
For the alkali-free glass of composition containing alkaline earth oxide, it is exposed to SO at high temperature2Gas and/or SO3In gas atmosphere
In the case of, the sulfate of alkaline-earth metal is salted out instead of alkali metal sulphuric acid, but its amount of precipitation is few, forms antisitic defect protective layer
Need the SO for being exposed to higher temperature, longer time or higher concentration2Gas and/or SO3In gas.But human hair of the present invention
It is existing, by the micro addition alkali metal oxide in glass raw material, the thus precipitation effect enhancing of alkali earth metal sulfate, to
Efficiency when forming antisitic defect protective layer on glass tape improves.
Here, when the content of alkali metal oxide increases, alkali metal ion is diffused into film and membrane property is made to deteriorate, because
This becomes problem in the use as various base plate for displaying glass, but if the alkali metal oxide in glass composition
Content is 2000 molar ppms hereinafter, not will produce this problem then.More preferably 1500 molar ppms are hereinafter, further preferably
For 1300 molar ppms hereinafter, below particularly preferably 1000 molar ppms.
The glass raw material used in the present invention contain preferably 1500 molar ppms or less, more preferably 1300 molar ppms with
Under, further preferably 1000 molar ppms alkali metal oxide below, further preferably 700~900 molar ppms, more
Preferably comprise 700~800 molar ppms.
In addition, as alkali metal oxide, from the effect for improving the efficiency when forming antisitic defect protective layer on glass tape
From the viewpoint of the balance of fruit and cost of material, preferably Na2O、K2O, more preferable Na2O。
It should be noted that in order not to be set to when panel manufactures the metal or sull of glass surface
Deterioration in characteristics, glass raw material is preferably substantially free from there is P2O5.In addition, in order to make glass be easy to recycle, the preferred base of glass raw material
PbO, As are not contained in sheet2O3、Sb2O3。
In addition, for the same reason, preferably substantially free from there is P2O5.Mixed volume as impurity is preferably 23 moles
Ppm hereinafter, more preferably 18 molar ppms hereinafter, further preferably 11 molar ppms hereinafter, particularly preferably 5 molar ppms with
Under.
For the melting for improving glass, clarification, formability, it is 1% or less, preferably that can contain in the total amount
0.5% ZnO, Fe below2O3、SO3、F、Cl、SnO2.ZnO is preferably substantially free from having.
The melting of above-mentioned glass composition is relatively low, therefore it is preferable to use following raw materials as each ingredient.
(silicon source)
As SiO2Silicon source, can use silica sand, use median particle diameter D50For 20 μm~60 μm, 5 μm of grain size it is below
The ratio of particle be the ratio of the particle of 100 μm of 0.3 volume % or less and grain size or more be 2.5 volume % silica sands below by
Make its fusing in the cohesion that can inhibit silica sand, therefore, the fusing of silica sand becomes easy, and can obtain that bubble is few, homogeneous
Property, the high plate glass of flatness, therefore preferably.
It should be noted that the ball equivalent diameter that " grain size " in this specification refers to silica sand (is primary in the present invention
The meaning of grain size), specifically, referring to the grain size in the size distribution using the powder of laser diffraction/scattering method measurement.
In addition, " the median particle diameter D in this specification50" refer to using laser diffractometry measure powder size distribution
In, more than the particle of a certain grain size volume frequency account for whole powders volume frequency 50% grain size.In other words, refer to
Grain size when cumulative frequency is 50% in the size distribution of the powder measured using laser diffractometry.
In addition, " ratio of 5 μm of particles below of grain size " in this specification and the " ratio of the particle of 100 μm of grain size or more
Example " for example measures size distribution to be measured by using laser diffraction/scattering method.
If the median particle diameter D of silica sand50For 30 μm hereinafter, then the fusing of silica sand become easier to, therefore more preferably.
In addition, in order to reduce flying upward for silica sand when fusing, the ratio of 5 μm of particles below of grain size in particularly preferred silica sand
Example is 0%.
In addition, the ratio of the particle of 100 μm of grain size in silica sand or more is 0% the fusing of silica sand to be made to be easier, thus it is special
Not not preferably.
(alkaline earth metal source)
As alkaline earth metal source, alkaline earth metal compound can be used.Here, as the specific of alkaline earth metal compound
Example, may be exemplified MgCO3、CaCO3、BaCO3、SrCO3、(Mg,Ca)CO3Carbonate such as (dolomites), MgO, CaO, BaO, SrO etc.
Oxide, Mg (OH)2、Ca(OH)2、Ba(OH)2、Sr(OH)2Equal hydroxide, part or all of alkaline earth metal source contain
The hydroxide of alkaline-earth metal is due to SiO when glass raw material melts2The unfused amount of ingredient reduce and it is preferred that.Contain in silica sand
SiO2When the unfused amount of ingredient increases, the unfused SiO2It is ingested to the bubble when generating bubble in melten glass
In and be gathered near the surface layer of melten glass.As a result, between the part other than the surface layer of melten glass and surface layer, SiO2's
Ratio of components generates difference, and the homogenieity of glass reduces, and flatness also reduces.
The content of the hydroxide of alkaline-earth metal (is scaled MO, wherein M is alkali in 100 mass mole % of alkaline earth metal source
Earth metal element) in preferably 12~90 moles of % (being scaled MO), more preferably 30~85 moles of % (being scaled MO), into one
Step is preferably 60~80 moles of % (being scaled MO) due to SiO when glass raw material melts2The unfused amount of ingredient reduce and more
It is preferred that.
Increase with the molar ratio of the hydroxide in alkaline earth metal source, SiO when glass raw material melts2Ingredient does not melt
Change amount reduces, and therefore, the higher the better for the molar ratio of above-mentioned hydroxide.
As alkaline earth metal source, specifically, mixture, the list of the hydroxide and carbonate of alkaline-earth metal can be used
The hydroxide etc. of only alkaline-earth metal.As carbonate, it is preferable to use MgCO3、CaCO3(Mg, Ca) (CO3)2(dolomite)
In any one more than.In addition, the hydroxide as alkaline-earth metal is, it is preferable to use Mg (OH)2Or Ca (OH)2In at least
One particularly preferably uses Mg (OH)2。
(boron source)
Contain B in above-mentioned glass composition2O3In the case of, as B2O3Boron source, boron compound can be used.Here, making
For the concrete example of boron compound, ortho-boric acid (H can be enumerated3BO3), metaboric acid (HBO2), tetraboric acid (H2B4O7), boric anhydride
(B2O3) etc..In the manufacture of common alkali-free glass, from cheap and from the viewpoint of being easy to get, ortho-boric acid is used.
In the present invention, as boron source, it is preferable to use (being scaled B in 100 mass % of boron source2O3) in contain 10~100 matter
Amount % (is scaled B2O3) boric anhydride boron source.By the way that boric anhydride is set as 10 mass % or more, glass raw material can inhibit
Cohesion, and the effect of bubble can be reduced, improve homogenieity, the effect of flatness.Boric anhydride is more preferably 20~100 matter
Measure %, further preferably 40~100 mass %.
As the boron compound other than boric anhydride, from cheap and from the viewpoint of being easy to get, preferred ortho-boric acid.
The manufacture of plate glass is for example implemented according to following step.
The raw material of each ingredient is allocated to become target component, it is continuously put into melting furnace, and it is heated to 1500~
1800 DEG C and melt.By the way that the melten glass to be configured to the glass tape of the plate of regulation plate thickness using building mortion, and should
It is cut after glass tape slow cooling, it is hereby achieved that plate glass.
In the present invention, it is preferred to utilize the glass tape that float forming is plate.
In the present invention, in leer, sulfurous acid is supplied to glass tape in a manner of meeting condition as follows
(SO2) and/or SO3Gas.
The strain point of alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C, so that
The mode that the time that the gas concentration directly below of the lower surface of glass tape reaches 500~20000ppm is 30 seconds or more supplies
SO2And/or SO3Gas.When gas concentration is less than 500ppm, it is possible to which the amount of precipitation of the sulfate of alkaline-earth metal is reduced.More preferably
For 1000ppm or more.When gas concentration is more than 20000ppm, it is possible to which the corrosion of equipment becomes problem.More preferably
10000ppm is hereinafter, further preferably 5000ppm or less.In addition, when less than 30 seconds, it is possible to the sulfate of alkaline-earth metal
Amount of precipitation is reduced.More preferably 1 minute or more.
In the present invention, it is preferred to supply SO from the lower surface of glass tape2And/or SO3Gas.By supplying SO from lower surface2
And/or SO3Gas, than heavy SO2And/or SO3Gas only makes the sulfuric acid of alkaline-earth metal salt out in lower surface, so as to
Prevent gas diffusion, improve alkaline-earth metal sulfate precipitation effect.
In the present invention, it is preferred to make glass tape and SO in the atmosphere that vapor dew point is 30 DEG C or more2And/or SO3Gas
Contact.When vapor dew point is low, it is possible to the precipitation effect of the sulfate of alkaline-earth metal can not be improved.More preferably 40 DEG C with
On, further preferably 50 DEG C or more.
It should be noted that can contain SO in above-mentioned atmosphere2Gas is oxidized into SO3Obtained from SO3Gas.
The strain point of the alkali-free glass of the present invention is 680 DEG C or more and 735 DEG C or less.
Since the strain point of the alkali-free glass of the present invention is 680 DEG C or more, heat when panel can be inhibited to manufacture is received
Contracting.Furthermore it is possible to which application is using the method for laser annealing as the manufacturing method of p-Si TFT.More preferably 685 DEG C or more, into
One step is preferably 690 DEG C or more.
Due to the present invention alkali-free glass strain point be 680 DEG C or more, be suitable for high strain-point purposes (for example,
Plate thickness is the base plate for displaying or photograph of 0.7mm or less, preferably 0.5mm or less, more preferably 0.3mm organic EL below
It is bright with substrate or plate thickness be 0.3mm or less, preferably 0.1mm thin plates below base plate for displaying or illumination base
Plate).
Plate thickness be 0.7mm or less, be further 0.5mm or less, be further 0.3mm or less, be further 0.1mm with
Under plate glass forming in, there are the tendencies that pull-out speed when forming is accelerated, and therefore, the fictive temperature of glass increases,
The shrinking percentage of glass is easy to increase.In this case, be high strain-point glass when, shrinking percentage can be inhibited.
On the other hand, due to strain point be 735 DEG C hereinafter, it is therefore not necessary to will in float tank and float tank outlet temperature
Be set to it is too high, in float tank and the service life of the metal component in float tank downstream side generate influence it is few.More preferably
725 DEG C hereinafter, further preferably 715 DEG C hereinafter, particularly preferably 710 DEG C or less.
In addition, in order to improve the plane strain of glass, need to carry being exported at the part into leer from float tank
High-temperature, but it is too high it is not necessary that temperature at this time to be set to.Therefore, load will not be applied to heater used in heating, it is right
The influence that heater life generates is few.
In addition, ordering the same reason for strain, the glass transition temperature of alkali-free glass of the invention is preferably 730
DEG C or more, more preferably 740 DEG C or more, further preferably 750 DEG C or more.Additionally, it is preferred that for 780 DEG C hereinafter, further excellent
775 DEG C are selected as hereinafter, particularly preferably 770 DEG C or less.
In addition, mean thermal expansion coefficients of the alkali-free glass of the present invention at 50~350 DEG C are 30 × 10-7~43 × 10-7/ DEG C, thermal shock resistance is big, and can improve productivity when panel manufacture.In the alkali-free glass of the present invention, at 50~350 DEG C
Mean thermal expansion coefficients be preferably 35 × 10-7/ DEG C or more.Mean thermal expansion coefficients at 50~350 DEG C are preferably 42 × 10-7/ DEG C hereinafter, more preferably 41 × 10-7/ DEG C hereinafter, further preferably 40 × 10-7/ DEG C or less.
In addition, the present invention alkali-free glass proportion be preferably 2.62 hereinafter, more preferably 2.60 hereinafter, further preferably
It is 2.58 or less.
In addition, the viscosities il of the alkali-free glass of the present invention reaches 102Moor temperature T when (dPas)2For 1710 DEG C hereinafter, more
Preferably 1700 DEG C hereinafter, further preferably 1690 DEG C hereinafter, particularly preferably 1680 DEG C or less, 1670 DEG C hereinafter, therefore
Fusing is easier.
In addition, the viscosities il of the alkali-free glass of the present invention reaches 104Temperature T when pool4For 1310 DEG C hereinafter, preferably 1305
DEG C hereinafter, more preferably 1300 DEG C hereinafter, further preferably less than 1300 DEG C, 1295 DEG C or less, 1290 DEG C hereinafter, be suitable for
Float forming.
In addition, the devitrification temperature of the alkali-free glass of the present invention for 1315 DEG C or less due to easy be formed using float glass process and
It is preferred that.Preferably 1300 DEG C or less, less than 1300 DEG C, 1290 DEG C hereinafter, more preferably 1280 DEG C or less.In addition, as float glass process
The temperature T of formability, the substantially standard of melt forming4(glass viscosity η reaches 104Temperature, unit when pool：DEG C) and devitrification
Temperature difference (T4Devitrification temperature) preferably -20 DEG C or more, -10 DEG C or more, further be 0 DEG C or more, more preferably 10 DEG C with
On, further preferably 20 DEG C or more, particularly preferably 30 DEG C or more.
Devitrification temperature in this specification is：Glass particle after crushing is put into the ware of platinum, is certain in control
The heat treatment that 17 hours are carried out in the electric furnace of temperature, by the optical microphotograph sem observation after heat treatment, on the surface of glass and interior
The average value of maximum temperature and the minimum temperature not precipitated crystal that portion precipitates crystal.
In addition, the Young's modulus of the alkali-free glass of the present invention is preferably 78GPa or more, more preferably 79GPa or more,
80GPa or more is even more preferably 81GPa or more, further preferably 82GPa or more.
In addition, the photoelastic constant of the alkali-free glass of the present invention is preferably 31nm/MPa/cm or less.
Liquid crystal display panel manufacturing process, liquid crystal display device using when the stress that generates to cause glass substrate to have two-fold
Penetrating property confirms the phenomenon that black display becomes grey, the contrast of liquid crystal display reduces sometimes as a result,.By will be photoelastic
Property constant is set as 31nm/MPa/cm hereinafter, can inhibit the phenomenon smaller.Preferably 30nm/MPa/cm is hereinafter, more excellent
29nm/MPa/cm is selected as hereinafter, further preferably 28.5nm/MPa/cm is hereinafter, particularly preferably 28nm/MPa/cm or less.
Furthermore, it is contemplated that other physical property ensure easiness when, the photoelastic constant of alkali-free glass of the invention is preferably
23nm/MPa/cm or more, more preferably 25nm/MPa/cm or more.
It should be noted that photoelastic constant can be measured by disk compression method in the case where measuring wavelength 546nm.
In addition, the relative dielectric constant of the glass of the present invention is preferably 5.6 or more.
Embedded touch control panel as recorded in Japanese Unexamined Patent Publication 2011-70092 bulletins is (in liquid crystal display panel
Inside it is built-in with the touch panel of touch sensor) in the case of, from sensing sensitivity, the reduction drive for improving touch sensor
Dynamic voltage is saved from the perspective of electric power, and the relative dielectric constant height of glass substrate is preferably.By the way that relative dielectric constant is set
It is 5.6 or more, the sensing sensitivity of touch sensor improves.Preferably 5.8 or more, more preferably 6.0 or more, it is further excellent
It is selected as 6.2 or more, particularly preferably 6.4 or more.
It should be noted that the method that relative dielectric constant can be recorded by JIS C-2141 is measured.
Embodiment
(Examples 1 to 9, comparative example 1~3)
It allocates the raw material of each ingredient and is formed with becoming target shown in table 1, melted in continuous fusion kiln, and utilize
Float glass process carries out plate forming.By the Na as the content of the alkali metal oxide in the raw material used at this time2The content of O, conduct
The median particle diameter D of the granularity of silica sand in used raw material50, 5 μm of particles below of grain size 100 μm of ratio and grain size
The ratio of above particle is shown in Table 1 together.In addition, by the molar ratio (conversion of the hydroxide source in alkaline-earth metal
For MO) also it is shown in Table 1 together.
After being mirror-finished to obtained glass, heat treatment temperature, heat treatment time, SO shown in table 22With/
Or SO3In SO under gas concentration, vapor dew point2And/or SO3It is heat-treated in gas atmosphere.The surface of obtained glass
Sulfuric acid salt out situation to be obtained using fluorescent X-ray surface S concentration (quality %) in the form of be measured.Glass is answered
Height, surface S concentration (quality %) are also shown in Table 2 together.It is calculating with the value that bracket indicates it should be noted that in table 2
Value.
[utilizing the assay method of the surface S concentration of fluorescent X-ray]
For the glass specimen of sulfate has been precipitated, the mask of φ 10mm is used to measure S-k α under the conditions shown in Table 3
The counting of ray.After being mirror-finished to glass known to S concentration, the mask of φ 10mm is used under the conditions shown in Table 3
The Alpha-ray countings of S-k are measured, to obtain the correlativity of S-k Alpha-ray counting and S concentration (quality %).By using institute
The S-k alpha ray counters for the glass specimen that sulfate has been precipitated are scaled S concentration (quality %) by obtained correlativity.Surface
S concentration is preferably 0.5 mass % or more, more preferably 0.6 mass % or more.
Table 3
| Device | Co., Ltd. Neo-Confucianism manufactures ZSX100e |
| Input | Rh 30kV-120mA |
| Optical filter | It closes |
| Attenuator | 1/1 |
| Slit | Standard |
| Analyzing crystal | RX9 |
| Detector | PC |
| PHA | 150-300 |
| 2 θ of peak/deg. (minute) | (105.900 30 seconds) |
| B.G.2 θ/deg. (minute) | (109.000 30 seconds) |
It is described the invention in detail with reference to specific embodiment, but aobvious and easy to those skilled in the art
See, can make various changes, correct without departing from the spirit and scope of the present invention.
The Japanese patent application 2013-235315 that the application was proposed based on November 13rd, 2013, and using its content as
Reference is included in this specification.
Industrial applicability
The strain point of the plate glass obtained through the invention is high, is suitable for base plate for displaying, base board for optical mask etc.
Purposes.In addition, being also adapted to the purposes such as substrate used for solar batteries.
Claims (9)
1. a kind of plate glass manufacturing method, wherein melt glass raw material and melten glass is made, and the melten glass is sharp
It is configured to the glass tape of plate with building mortion, the glass tape is then subjected to slow cooling, the plate glass using annealing device
In manufacturing method,
The plate glass includes following alkali-free glasss,
The strain point of the alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C, so that
The SO directly below of the lower surface of the glass tape2The time that gas concentration reaches 500~20000ppm is 30 seconds or more
Mode supplies SO2Gas,
The strain point of the alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7~43
×10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104When dPas
Temperature T4Less than 1300 DEG C, indicate that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.4 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
2. a kind of plate glass manufacturing method, wherein melt glass raw material and melten glass is made, and the melten glass is sharp
It is configured to the glass tape of plate with building mortion, the glass tape is then subjected to slow cooling, the plate glass using annealing device
In manufacturing method,
The plate glass includes following alkali-free glasss,
The strain point of the alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C, so that
The SO directly below of the lower surface of the glass tape3The time that gas concentration reaches 500~20000ppm is 30 seconds or more
Mode supplies SO3,
The strain point of the alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7~43
×10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104When dPas
Temperature T4Less than 1300 DEG C, indicate that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.4 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
3. a kind of plate glass manufacturing method, wherein melt glass raw material and melten glass is made, and the melten glass is sharp
It is configured to the glass tape of plate with building mortion, the glass tape is then subjected to slow cooling, the plate glass using annealing device
In manufacturing method,
The plate glass includes following alkali-free glasss,
The strain point of the alkali-free glass is being set as TstWhen (DEG C), in Tst+ 70 DEG C~TstWithin the temperature range of -50 DEG C, so that
The SO directly below of the lower surface of the glass tape2And SO3Gas concentration reach 500~20000ppm time be 30 seconds with
On mode supply SO2And SO3Gas,
The strain point of the alkali-free glass is that the mean thermal expansion coefficients at 680~735 DEG C, 50~350 DEG C are 30 × 10-7~43
×10-7/ DEG C, glass viscosity reaches 102Temperature T when dPas2For 1710 DEG C hereinafter, glass viscosity reaches 104When dPas
Temperature T4Less than 1300 DEG C, indicate that the alkali-free glass contains with mole % based on oxide：
MgO+CaO+SrO+BaO is 15.5~21,
MgO/ (MgO+CaO+SrO+BaO) is 0.4 or more,
CaO/ (MgO+CaO+SrO+BaO) be 0.50 hereinafter,
SrO/ (MgO+CaO+SrO+BaO) is 0.50 or less.
4. plate glass manufacturing method as described in claim 1, wherein the alkali-free glass contains 500~2000 molar ppms
Alkali metal oxide.
5. plate glass manufacturing method as claimed in claim 2 or claim 3, wherein the alkali-free glass contains 150~2000 moles
The alkali metal oxide of ppm.
6. plate glass manufacturing method as described in any one of claims 1 to 4, wherein the building mortion be float glass process at
Shape dress is set.
7. plate glass manufacturing method as described in any one of claims 1 to 4, wherein as SiO2The silicon source of raw material, makes
With median particle diameter D50Ratio for 5 μm of 20 μm~60 μm, grain size particles below be 0.3 volume % or less and 100 μm of grain size with
On particle ratio be 2.5 volume % silica sands below.
8. plate glass manufacturing method as described in any one of claims 1 to 4, wherein as MgO, CaO, SrO and BaO
Alkaline earth metal source, using in 100 moles of % of the alkaline earth metal source to be converted with MO containing with MO being scaled 12~90 moles of %
Alkaline-earth metal hydroxide alkaline earth metal source, wherein M be alkali earth metal.
9. plate glass manufacturing method as described in any one of claims 1 to 4, wherein as SiO2The silicon source of raw material, makes
With median particle diameter D50Ratio for 5 μm of 20 μm~60 μm, grain size particles below be 0.3 volume % or less and 100 μm of grain size with
On particle ratio be 2.5 volume % silica sands below；As the alkaline earth metal source of MgO, CaO, SrO and BaO, using with
Hydroxide containing the alkaline-earth metal for being scaled 15~100 moles of % with MO in 100 moles of % of alkaline earth metal source of MO conversions
Alkaline earth metal source, wherein M be alkali earth metal.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013235315A JP2017007870A (en) | 2013-11-13 | 2013-11-13 | Manufacturing method of sheet glass |
| JP2013-235315 | 2013-11-13 | ||
| PCT/JP2014/079745 WO2015072429A1 (en) | 2013-11-13 | 2014-11-10 | Method for manufacturing sheet glass |
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| CN105722800A CN105722800A (en) | 2016-06-29 |
| CN105722800B true CN105722800B (en) | 2018-09-21 |
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| CN201480061692.9A Active CN105722800B (en) | 2013-11-13 | 2014-11-10 | The manufacturing method of plate glass |
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| JP (1) | JP2017007870A (en) |
| KR (1) | KR20160085260A (en) |
| CN (1) | CN105722800B (en) |
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| KR102249898B1 (en) * | 2013-11-28 | 2021-05-11 | 에이지씨 가부시키가이샤 | Alkali-free glass substrate and method for thinning alkali-free glass substrate |
| KR102292435B1 (en) | 2015-06-30 | 2021-08-20 | 아반스트레이트 가부시키가이샤 | Glass substrate for display and manufacturing method thereof |
| WO2017002808A1 (en) | 2015-06-30 | 2017-01-05 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate for display and method for producing same |
| JP6953944B2 (en) * | 2017-09-21 | 2021-10-27 | Ａｇｃ株式会社 | Borosilicate glass and its manufacturing method |
| KR102674809B1 (en) * | 2018-03-09 | 2024-06-14 | 에이지씨 가부시키가이샤 | Alkali-free glass substrate |
| WO2020162604A1 (en) * | 2019-02-07 | 2020-08-13 | Ａｇｃ株式会社 | Alkali-free glass |
| WO2020162606A1 (en) * | 2019-02-07 | 2020-08-13 | Ａｇｃ株式会社 | Alkali-free glass |
| US11718553B2 (en) | 2019-03-19 | 2023-08-08 | AGC Inc. | Alkali-free glass substrate |
| CN117164229A (en) * | 2019-04-12 | 2023-12-05 | Ａｇｃ株式会社 | Glass sheet and method for manufacturing same |
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| CN101808951A (en) * | 2007-10-25 | 2010-08-18 | 旭硝子株式会社 | Method for production of non-alkali glass |
| CN102092921A (en) * | 2009-12-14 | 2011-06-15 | 旭硝子株式会社 | Producing method and producing device of float glass |
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| JP3083586B2 (en) | 1991-04-26 | 2000-09-04 | 旭硝子株式会社 | Alkali-free glass |
| US5116789A (en) | 1991-08-12 | 1992-05-26 | Corning Incorporated | Strontium aluminosilicate glasses for flat panel displays |
| JP3800657B2 (en) * | 1996-03-28 | 2006-07-26 | 旭硝子株式会社 | Alkali-free glass and flat display panel |
| JP3804112B2 (en) | 1996-07-29 | 2006-08-02 | 旭硝子株式会社 | Alkali-free glass, alkali-free glass manufacturing method and flat display panel |
| JP4276021B2 (en) * | 2003-08-04 | 2009-06-10 | セントラル硝子株式会社 | Float glass plate for display substrate and manufacturing method thereof |
| WO2008004481A1 (en) * | 2006-07-07 | 2008-01-10 | Asahi Glass Co., Ltd. | Process for producing glass substrate for flat panel glass |
| JP2009148141A (en) | 2007-12-18 | 2009-07-02 | Sumitomo Electric Ind Ltd | Magnetic material component |
| CN102471134B (en) * | 2009-07-02 | 2015-04-15 | 旭硝子株式会社 | Alkali-free glass and method for producing same |
| JP5537144B2 (en) * | 2009-12-16 | 2014-07-02 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass composition and glass substrate for flat panel display using the same |
| KR20130100244A (en) * | 2010-07-26 | 2013-09-10 | 아사히 가라스 가부시키가이샤 | Glass substrate for cu-in-ga-se solar battery, and solar battery using same |
| WO2013005402A1 (en) * | 2011-07-01 | 2013-01-10 | ＡｖａｎＳｔｒａｔｅ株式会社 | Glass substrate for flat panel display and production method therefor |
| JP2013107801A (en) * | 2011-11-22 | 2013-06-06 | Nippon Electric Glass Co Ltd | Method for producing glass substrate |
| JPWO2013172307A1 (en) * | 2012-05-16 | 2016-01-12 | 旭硝子株式会社 | Sheet glass manufacturing method |
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| CN101808951A (en) * | 2007-10-25 | 2010-08-18 | 旭硝子株式会社 | Method for production of non-alkali glass |
| CN102092921A (en) * | 2009-12-14 | 2011-06-15 | 旭硝子株式会社 | Producing method and producing device of float glass |
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| WO2015072429A1 (en) | 2015-05-21 |
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| KR20160085260A (en) | 2016-07-15 |
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